Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
366(6), P. 1331 - 1340
Published: Nov. 14, 2023
Abstract
Herein
we
report
that
cycloheptatrienyl‐substituted
1,5‐diynes
with
aromatic
backbones
undergo
a
gold‐catalysed
5‐
endo
‐
dig
cyclisation
to
give
11
H
‐indeno‐[2,1‐
]azulenes
at
room
temperature.
This
methodology
complements
the
established
range
of
structures
obtained
from
conversions
differently
substituted
accessed
via
highly
reactive
cationic
intermediates.
We
have
demonstrated
scope
reaction
and
assessed
possibility
further
functionalisation
indenoazulene
scaffold.
Additionally,
studied
optical
electrochemical
properties
as
well
frontier
molecular
orbitals
this
structural
motif
by
both
spectroscopic
theoretical
means.
Advanced Functional Materials,
Journal Year:
2023,
Volume and Issue:
34(6)
Published: Oct. 22, 2023
Abstract
To
mimic
biological
systems'
healing
mechanism
and
sensory
motion,
the
combination
of
self‐healing,
perception,
actuation
in
a
singular
soft
artificial
material
is
required,
which
would
be
enormously
valuable
for
robotics
that
commit
to
obtaining
multifunction
local
sensing
capacities
approaching
living
organisms.
However,
most
existing
somatosensory
actuators
lack
self‐healing
capability
injuries,
suffer
from
insufficient
actuating
performance
sensitivity,
complicated
manufacturing
operations.
Herein,
bioinspired
conductive
photo‐responsive
architecture
reported.
Rapidly
anthracene,
matrix
with
dynamic
interactions,
high‐conductivity
slideable
silver
nanowires
chemically
integrated
are
respectively
utilized
neuromuscular
system
effectors,
tissue
systems,
nerve
cords
receptors
octopus
tentacles.
Such
actuator
exhibits
rapid
(light‐driven
bending
velocity,
10
o
s
−1
),
distinctive
intrinsic
strain
sensitivity
(gauge
factor,
90.88),
decent
efficiency
(92.2%).
As
proof
concept,
octopi
tentacles‐inspired
smart
grippers
fabricated
various
motions
including
bending,
weightlifting
object
grasping
can
contemporaneously
detect
actions
by
real‐time
resistance
changes
provide
information
feedback.
This
work
anticipated
bring
fresh
horizons
design
multifunctional
materials
establish
pathway
advancement
self‐diagnostic
robots.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(23)
Published: March 30, 2023
Axially
chiral
biaryls
widely
exist
in
natural
products
and
pharmaceuticals
are
used
as
ligands
catalysts
asymmetric
synthesis.
Compared
to
the
well-established
axially
6-membered
biaryl
skeletons,
examples
of
5-membered
have
been
quite
scarce,
mono-substituted
3-arylpyrrole
atropisomers
not
reported.
Here,
we
disclose
a
copper-catalyzed
atroposelective
diyne
cyclization
for
construction
range
arylpyrrole
good
excellent
yields
with
generally
enantioselectivities
via
oxidation
X-H
insertion
vinyl
cations.
Importantly,
this
protocol
only
represents
first
synthesis
atropisomers,
but
also
constitutes
example
atropisomer
Theoretical
calculations
further
support
mechanism
cation-involved
elucidate
origin
enantioselectivity.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(10)
Published: Jan. 14, 2023
[2,3]-Sigmatropic
rearrangement
reaction
involving
sulfonium
ylide
(Doyle-Kirmse
reaction)
generated
from
metal
carbenes
represents
one
of
the
powerful
methods
for
construction
C(sp3
)-S
and
C-C
bonds.
Although
significant
advances
have
been
achieved,
asymmetric
versions
via
generation
ylides
rarely
reported
to
date,
they
so
far
limited
diazo
compounds
as
carbene
precursors.
Here,
we
describe
a
copper-catalyzed
enantioselective
Doyle-Kirmse
azide-ynamide
cyclization,
leading
practical
divergent
assembly
an
array
chiral
[1,4]thiazino[3,2-b]indoles
bearing
quaternary
carbon
stereocenter
in
generally
moderate
excellent
yields
enantioselectivities.
Importantly,
this
protocol
unique
catalytic
non-diazo
approach
unprecedented
[2,3]-sigmatropic
α-imino
carbenes.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 9, 2023
The
C-N
axially
chiral
N-arylpyrrole
motifs
are
privileged
scaffolds
in
numerous
biologically
active
molecules
and
natural
products,
as
well
ligands/catalysts.
Asymmetric
synthesis
of
N-arylpyrroles,
however,
is
still
challenging,
the
simultaneous
creation
contiguous
axial
central
chirality
remains
unknown.
Herein,
a
diastereo-
atroposelective
N-arylpyrroles
enabled
by
light-induced
phosphoric
acid
catalysis
has
been
developed.
key
transformation
one-pot,
three-component
oxo-diarylation
reaction,
which
simultaneously
creates
quaternary
stereogenic
center.
A
broad
range
unactivated
alkynes
were
readily
employed
reaction
partner
this
transformation,
products
obtained
good
yields,
with
excellent
enantioselectivities
very
diastereoselectivities.
Notably,
skeletons
represent
interesting
structural
that
could
be
used
ligands
catalysts
asymmetric
catalysis.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: March 12, 2024
Site-
and
stereoselective
C-H
functionalization
is
highly
challenging
in
the
synthetic
chemistry
community.
Although
of
vinyl
cations
has
been
vigorously
studied
C(sp
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 9, 2025
Transition-metal-catalyzed
[2
+
2
2]
annulation
of
alkynes
is
an
efficient
pathway
for
the
synthesis
aromatic
compounds.
However,
most
established
methods
require
noble
metal
catalysts.
Herein,
we
report
a
copper-catalyzed
intermolecular
diynes
with
through
vinyl
cation
intermediates,
enabling
atom-economical
preparation
biologically
important
carbazole
skeletons.
The
reaction
shows
good
regioselectivity
in
aryl(alkyl)alkynes.
Moreover,
preliminary
results
have
also
been
obtained
related
catalytic
atroposelective
transformation.
This
represents
rare
example
non-noble-metal-catalyzed
ynamides
pathway.
Science Advances,
Journal Year:
2023,
Volume and Issue:
9(11)
Published: March 15, 2023
In
the
past
two
decades,
substantial
advances
have
been
made
on
asymmetric
alkyne
functionalization
by
activation
of
inert
alkynes.
However,
these
transformations
so
far
mostly
limited
to
transition
metal
catalysis,
and
chiral
Brønsted
acid-catalyzed
examples
are
rarely
explored.
Here,
we
report
a
dearomatization
reaction
phenol-
indole-tethered
homopropargyl
amines,
allowing
practical
atom-economical
synthesis
diverse
array
valuable
fused
polycyclic
enones
indolines
bearing
quaternary
carbon
stereocenter
contiguous
stereogenic
centers
in
moderate
good
yields
with
excellent
diastereoselectivities
generally
enantioselectivities
(up
>99%
enantiomeric
excess).
This
protocol
demonstrates
dearomatizations
via
vinylidene-quinone
methides.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Nov. 3, 2023
The
formal
C-C
bond
insertion
into
aldehydes
is
an
attractive
methodology
for
the
assembly
of
homologated
carbonyl
compounds.
However,
homologation
has
been
limited
to
diazo
approach
and
enantioselective
reaction
was
rarely
developed.
Herein,
we
report
asymmetric
through
diyne
cyclization
strategy.
In
presence
Cu(I)/SaBOX
catalyst,
this
method
leads
efficient
construction
versatile
axially
chiral
naphthylpyrroles
in
moderate
excellent
yields
with
good
enantioselectivities.
This
protocol
represents
a
rare
example
using
non-diazo
approach.
combined
experimental
computational
mechanistic
studies
reveal
mechanism,
origin
regioselectivity
stereoselectivity.
Notably,
phosphine
ligand
derived
from
synthesized
skeleton
proven
be
applicable
catalysis.
